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81.
82.
A quantum-mechanical model for the theoretical calculation of optical activity in “pseudo” π-systems is presented. Based on refined one-dimensional electron gas theory, the model allows for a rapid evaluation of electric and magnetic transition moments and of origin-independent rotational strengths. The influence of varying wave functions and geometry on the rotational strengths of skew butadiene conformations is discussed. 相似文献
83.
This experiment examined the generation of virtual pitch for harmonically related tones that do not overlap in time. The interval between successive tones was systematically varied in order to gauge the integration period for virtual pitch. A pitch discrimination task was employed, and both harmonic and nonharmonic tone series were tested. The results confirmed that a virtual pitch can be generated by a series of brief, harmonically related tones that are separated in time. Robust virtual pitch information can be derived for intervals between successive 40-ms tones of up to about 45 ms, consistent with a minimum estimate of integration period of about 210 ms. Beyond intertone intervals of 45 ms, performance becomes more variable and approaches an upper limit where discrimination of tone sequences can be undertaken on the basis of the individual frequency components. The individual differences observed in this experiment suggest that the ability to derive a salient virtual pitch varies across listeners. 相似文献
84.
Inclusion Complexes of Dyes and Cyclodextrins: Modeling Supermolecules by Rigorous Quantum Mechanics
W.A. Adeagbo V. Buss P. Entel 《Journal of inclusion phenomena and macrocyclic chemistry》2002,44(1-4):203-205
The results of structure optimization and molecular dynamics simulationof host-guest -cyclodextrin-pinacyanol dye inclusion complexesare obtained by applying a density functional based tight-binding code.The results attempt to correlate UV/Vis and circular dichroism spectraldata with calculated aggregate structures of the sandwich dimer, withthe monomers twisted slightly against each other. The sense of twist ispredetermined by the chirality of the complexing host. The UV/Vis-spectralare interpreted using the exciton model. Within this model, each excitedstate of the monomer generates two excitonic states in the dimer. Theinteraction between the two monomers results then in a Davydov splittingof the two dimer states. The opposite signs of the two dimer states can beattributed to the twist of the monomers when they interact. 相似文献
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Introduction of masker amplitude modulation (AM) can improve signal detection in a number of paradigms. In some cases this advantage depends on the coherence of modulation across a relatively wide frequency range. In the experiments described below, observers were asked to identify masked spondee words produced by a single male talker. The target spondees and masking noise were filtered into nine narrow bands, and the coherence of AM of either the speech signal or noise masker was manipulated. Inherent modulation of the masker bands was manipulated via assignment of real and imaginary values to the associated components of each band in the frequency domain, and AM of speech bands was achieved via multiplication with envelopes extracted from these maskers. Responses were based on two alternatives, four alternatives, or open response sets. The effect of masker AM coherence was highly dependent upon the size of the response set: coherent AM was associated with better thresholds in a two-alternative response set, but poorer thresholds in an open response set. Results with AM speech did not depend critically upon the across-frequency temporal synchrony of AM imposed on the speech material. 相似文献
87.
The present study investigated the hypothesis that the cues for modulation rate discrimination for unresolved spectral components differ as a function of the spectral region occupied by the stimuli. Specifically, it was hypothesized that when components occupy relatively low spectral regions, phase locking both to the fine structure and to the envelope are useful cues. However, as the spectral region occupied by the components increases, phase locking to the fine structure becomes less robust, whereas phase locking to the envelope remains as a potentially strong cue. Observers were asked to detect a decrease in modulation rate for carrier frequencies between 1500 and 6000 Hz. Both amplitude-modulated (AM) and quasifrequency-modulated (QFM) tones were used in order to produce stimuli having strong and weak envelope cues, respectively. Although there were marked individual differences, the results showed an interaction between modulation type and spectral region, with AM and QFM performance being relatively similar at low spectral region, but with QFM showing a steeper reduction in performance as the spectral region of the carrier frequency increased. Overall, the data are consistent with an interpretation that pitch perception for unresolved components depends upon both fine structure and envelope cues, and that the relative importance of these cues depends upon the spectral region occupied by the stimuli. 相似文献
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E Adjaye-Mensah WG Gonzalez DR Bussé B Captain J Miksovska JN Wilson 《The journal of physical chemistry. A》2012,116(34):8671-8677
The photophysics of 1-ethyl-4,6-bis(4-methoxyphenyl)-2(1H)-pyrimidone (1) and 1-ethyl-4,6-bis(4-(dimethylamino)phenyl)-2(1H)-pyrimidone (2) were investigated to determine the mechanisms of emission switching in response to protonation. UV-vis and steady state emission spectroscopy of the protonated and unprotonated forms across a range of solvents reveal the polarity dependence of the vertical excitation energies. Emission lifetimes and quantum yields show the solvent dependency of the excited states. Emission enhancements were observed in polyethylene glycol solutions and in the solid state (both thin film and single crystal), demonstrating the role of intramolecular rotation in thermal relaxation of the excited states. TD-DFT calculations provide insights into the excited state geometries and the role of intramolecular charge transfer. The collected data show that emission of diphenylpyrimidones can be modulated by four factors, including the identity of the electron-donating auxochrome, protonation state, solvent polarity, and viscosity. 相似文献